The invention relates to dibenzenic ortho-phenylenediamines comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring, and aliphatic chains comprising at least one quaternized unsaturated ring, to their use for the oxidation dyeing of keratin fibres, to dye compositions containing them, and to oxidation dyeing processes using them.
It is known practice to dye keratin fibres, and in particular human hair, with dye compositions containing oxidation dye precursors, in particular para-phenylenediamines, ortho-aminophenols or para-aminophenols and heterocyclic compounds such as diaminopyrazole derivatives, which are generally referred to as oxidation bases. The oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds which, when combined with oxidizing products, can give rise to coloured compounds and dyes by a process of oxidative condensation.
It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or coloration modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds.
The variety of molecules used as oxidation bases and couplers makes it possible to obtain a wide range of colours.
Oxidation dyes, by which so-called xe2x80x9cpermanentxe2x80x9d coloration can be obtained, must satisfy a certain number of requirements. Oxidation dyes should have no toxicological drawbacks, should allow shades of the desired strength to be obtained, and should have good resistance to external agents (e.g., light, bad weather, washing, permanent-waving, perspiration and friction).
The dyes should also allow white hairs to be covered, and should be as unselective as possible, i.e. they should allow the smallest possible differences in coloration to be produced over the entire length of the same keratin fibre, which may indeed be differently sensitized (i.e. damaged) between its tip and its root.
The inventors have discovered, surprisingly and unexpectedly, that a novel family of dibenzenic ortho-phenylenediamines of formula (I) defined below, comprising at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains comprising at least one quaternized saturated ring, and aliphatic chains comprising at least one quaternized unsaturated ring, are suitable for use as oxidation bases or as couplers or as self-oxidizing compounds for oxidation dyeing, and can also allow dye compositions to be obtained which can lead to strong colorations, in a wide range of shades, and which can have excellent properties of resistance to the various treatments to which keratin fibres may be subjected. These compositions can be readily synthesized.
These discoveries form the basis of the present invention.
A subject of the invention is thus ortho-phenylenediamines of formula (I) below, and the acid addition salts thereof: 
in which:
B is a linker arm chosen from linear and branched alkyl chains, which can be optionally interrupted with at least one group chosen from Z groups and hetero atoms such as oxygen, sulphur, and nitrogen, and which can be optionally substituted with at least one substituent chosen from hydroxyls and (C1-C6) alkoxys, and which can optionally bear at least one ketone function; in an embodiment of the invention, the alkyl chains comprise from 1 to 14 carbon atoms;
R1, R2, R3, Rxe2x80x21, Rxe2x80x22 and Rxe2x80x23, which may be identical or different, can be the point of attachment of a linker arm B, i.e., they represent one of the two valencies of linker arm B; otherwise, they are chosen from a hydrogen atom; halogens; Z groups; (C1-C6)alkylcarbonyls; amino(C1-C6)alkylcarbonyls; Nxe2x80x94Z-amino(C1-C6)-alkylcarbonyls; Nxe2x80x94(C1-C6)alkylamino(C1-C6)alkylcarbonyls; N,N-di(C1-C6)alkylamino(C1-C6)alkylcarbonyls; amino(C1-C6)alkylcarbonyl(C1-C6)alkyls; Nxe2x80x94Z-amino(C1-C6)alkylcarbonyl(C1-C6)alkyls; Nxe2x80x94(C1-C6)alkylamino(C1-C6)-alkylcarbonyl(C1-C6)alkyls; N,N-di(C1-C6)alkylamino(C1-C6)alkylcarbonyl-(C1-C6)alkyls; carboxyl; C1-C6)alkylcarboxyls; (C1-C6)alkylsulphonyls; aminosulphonyls; Nxe2x80x94Z-aminosulphonyls; (C1-C6)N-alkylaminosulphonyls; N,N-di(C1-C6)alkylaminosulphonyls; (C1-C6)aminosulphonylalkyls; (C1-C6)Nxe2x80x94Z-aminosulphonylalkyls; Nxe2x80x94(C1-C6)alkylaminosulphonyl(C1-C6)alkyls; N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyls; carbamyl; Nxe2x80x94(C1-C6)alkylcarbamyls; N,N-di(C1-C6)alkylcarbamyls; carbamyl(C1-C6)alkyls; Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyls; N,N-di(C1-C6)alkylcarbamyl(C1-C6)alkyls; (C1-C6)alkyls; (C1-C6)monohydroxyalkyls; (C2-C6)polyhydroxyalkyls;(C1-C6)alkoxy(C1-C6)alkyls; (C1-C6)trifluoroalkyls; cyano; OR6 and SR6 groups; amino groups protected with a radical chosen from (C1-C6)alkylcarbonyls, (C1-C6)alkylcarboxyls, trifluoro(C1-C6)alkylcarbonyls, amino(C1-C6)alkylcarbonyls, Nxe2x80x94Z-amino(C1-C6)alkylcarbonyls, Nxe2x80x94(C1-C6)alkylamino(C1-C6)alkylcarbonyls, N,N-di(C1-C6)alkylamino(C1-C6)alkylcarbonyls, (C1-C6)alkylcarboxyls, carbamyl, Nxe2x80x94(C1-C6)alkylcarbamyls, N,N-di(C1-C6)alkylcarbamyls, (C1-C6)alkylsulphonyls, aminosulphonyls, Nxe2x80x94Z-aminosulphonyls, (C1-C6)N-alkylaminosulphonyl, N,N-di(C1-C6)alkylaminosulphonyls, thiocarbamyl, formyl, and Z groups in which the linker arm B comprises a ketone function directly attached to the nitrogen atom of the amino group;
R6 can be the point of attachment of a linker arm B, i.e., it can be one of the two valencies of a linker arm; otherwise R6 is a radical chosen from (C1-C6)alkyls; (C1-C6)monohydroxyalkyls; (C2-C6)polyhydroxyalkyls; Z groups; (C1-C6)alkoxy(C1-C6)alkyls; aryls; benzyl; carboxy(C1-C6)alkyls; (C1-C6)alkylcarboxy(C1-C6)alkyls; cyano(C1-C6)alkyls; carbamyl(C1-C6)alkyls; Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyls; N,N-di(C1-C6)alkylcarbamyl(C1-C6)alkyls; (C1-C6)trifluoroalkyls; (C1-C6)aminosulphonylalkyls; (C1-C6)Nxe2x80x94Z-aminosulphonylalkyls; Nxe2x80x94(C1-C6)alkylaminosulphonyl(C1-C6)alkyls; N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyls; (C1-C6)alkylsulphinyl(C1-C6)alkyls; (C1-C6)alkylsulphonyl-(C1-C6)alkyls; (C1-C6)alkylcarbonyl(C1-C6)alkyls; (C1-C6)aminoalkyls; (C1-C6)aminoalkyls in which the amine is substituted with one or two identical or different radicals chosen from (C1-C6)alkyls, (C1-C6)monohydroxyalkyls, (C2-C6)polyhydroxyalkyls, (C1-C6)alkylcarbonyls, formyl, trifluoro-(C1-C6)alkylcarbonyls, (C1-C6)alkylcarboxyls, carbamyl, Nxe2x80x94(C1-C6)alkylcarbamyls, N,N-di-(C1-C6)alkylcarbamyls, thiocarbamyl, (C1-C6)alkylsulphonyls, and Z groups;
R4, R5, R7, R8, Rxe2x80x24, Rxe2x80x25, Rxe2x80x27 and Rxe2x80x28, which may be identical or different, can be the point of attachment of a linker arm B, i.e, they can represent one of the two valencies of a linker arm B; otherwise they are chosen from a hydrogen atom; Z groups; (C1-C6)alkyls;(C1-C6)monohydroxyalkyls; (C2-C6)polyhydroxyalkyls; (C1-C6)alkoxy(C1-C6)alkyls; aryls; benzyl; cyano(C1-C6)alkyls; carbamyl(C1-C6)alkyls; Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyls; N,N-di(C1-C6)alkylcarbamyl(C1-C6)alkyls; thiocarbamyl(C1-C6)alkyls; (C1-C6)trifluoroalkyls; (C1-C6)sulphoalkyls;(C1-C6)alkylcarboxy(C1-C6)alkyls; (C1-C6)alkylsulphinyl(C1-C6)alkyls; (C1-C6)aminosulphonylalkyls; (C1-C6) Nxe2x80x94Z-aminosulphonylalkyls; Nxe2x80x94(C1-C6)alkylaminosulphonyl(C1-C6)alkyls; N,N-di(C1-C6)alkylaminosulphonyl(C1-C6)alkyls; (C1-C6)alkylcarbonyl(C1-C6)alkyls; (C1-C6)aminoalkyls; (C1-C6)aminoalkyls in which the amine is substituted with one or two identical or different radicals chosen from (C1-C6)alkyls, (C1-C6) monohydroxyalkyls, (C2-C6)polyhydroxyalkyls, (C1-C6)alkylcarbonyls, carbamyl, Nxe2x80x94(C1-C6)alkylcarbamyls, N,N-di(C1-C6)alkylcarbamyls, (C1-C6)alkylsulphonyls, formyls, trifluoro(C1-C6)-alkylcarbonyls, (C1-C6)alkylcarboxyls, thiocarbamyl, and Z groups;
Z is chosen from unsaturated cationic groups of formulae (II) and (III) below, and saturated cationic groups of formula (IV) below: 
xe2x80x83in which:
D is a linker arm chosen from linear and branched alkyl chains, which are optionally interrupted by at least one hetero atom such as oxygen, sulphur and nitrogen, and which can optionally be substituted with at least one radical chosen from hydroxyls and (C1-C6)alkoxys, and which also can optionally bear at least one ketone function; in an embodiment of the invention, the alky chains comprise from 1 to 14 carbon atoms.
the ring members E, G, J, L and M, which may be identical or different, are
chosen from carbon, oxygen, sulphur and nitrogen atoms;
n is chosen from the integers 0, 1, 2, 3, and 4;
m is chosen from the integers 0, 1, 2, 3, 4, and 5;
the radicals R, which may be identical or different, can be the point of attachment of a linker arm B, i.e., they can represent one of the two valencies of a linker arm B; otherwise they are chosen from a second group Z which is identical to or different from the first group Z, halogen atoms, a hydroxyl group, (C1-C6)alkyls, (C1-C6)monohydroxyalkyls, (C2-C6)polyhydroxyalkyls, nitro, cyano, cyano(C1-C6)alkyls, (C1-C6)alkoxyls, tri(C1-C6)alkylsilane(C1-C6)alkyls, amido, aldehydo, carboxyl, (C1-C6)alkylcarbonyls, thio, (C1-C6)thioalkyls, (C1-C6)alkylthios, amino, aminos protected with a radical chosen from (C1-C6)alkylcarbonyls, carbamyl, and (C1-C6)alkylsulphonyls; NHRxe2x80x3 and NRxe2x80x3Rxe2x80x2xe2x80x3 groups in which Rxe2x80x3 and Rxe2x80x2xe2x80x3, which may be identical or different, are chosen from (C1-C6)alkyl radicals, (C1-C6)monohydroxyalkyl radicals and (C2-C6)polyhydroxyalkyl radicals;
R9 can be the point of attachment of a linker arm B, i.e., it can represent one of the two valencies of a linker arm B; otherwise R9 is a radical chosen from (C1-C6) alkyls, (C1-C6)monohydroxyalkyls, (C2-C6)polyhydroxyalkyls, cyano(C1-C6)alkyls, tri(C1-C6)alkylsilane(C1-C6)alkyls, (C1-C6)alkoxy(C1-C6)alkyls, carbamyl-(C1-C6)alkyls, (C1-C6)alkylcarboxy(C1-C6)-alkyls, benzyl, and a second group Z which is identical to or different from the first group Z;
R10, R11 and R12, which may be identical or different, can be the point of attachment of a linker arm B, i.e., it can represent one of the two valencies of a linker arm B; otherwise they are radicals chosen from (C1-C6)alkyls, (C1-C6)monohydroxyalkyls, (C2-C6)polyhydroxyalkyls, (C1-C6)alkoxy(C1-C6)alkyls, cyano(C1-C6)alkyls, aryls, benzyl, (C1-C6)amidoalkyls, tri(C1-C6)alkylsilane(C1-C6)alkyls, and (C1-C6)aminoalkyls in which the amine is protected with a radical chosen from (C1-C6)alkylcarbonyls, carbamyl, and (C1-C6)alkylsulphonyls; two of the radicals R10, R11 and R12 can together also form, with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring or a ring containing at least one additional hetero atom such as, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, it being possible for the ring to be unsubstituted or to be substituted with a substituent chosen from halogen atoms, a hydroxyl group, (C1-C6)alkyls, (C1-C6) monohydroxyalkyls, (C2-C6) polyhydroxyalkyls, nitro, cyano, cyano(C1-C6)alkyls, (C1-C6)alkoxys, tri(C1-C6)alkylsilane(C1-C6)alkyls, amido, aldehydo, carboxyl, keto(C1-C6)alkyls, thio, (C1-C6)thioalkyls, (C1-C6)alkylthios, amino, and aminos protected with a radical chosen from (C1-C6)alkylcarbonyls, carbamyls, and (C1-C6)alkylsulphonyls;
one of the radicals R10, R1, and R12 can also be chosen from a second group Z which is identical to or different from the first group Z;
R13 can be the point of attachment of a linker arm B, i.e., it can represent one of the two valencies of a linker arm B; otherwise R13 is a radical chosen from (C1-C6)alkyls; (C1-C6) monohydroxyalkyls; (C2-C6)polyhydroxyalkyls; aryls: benzyl; (C1-C6)aminoalkyls, (C1-C6)aminoalkyls in which the amine is protected with a radical chosen from (C1-C6)alkylcarbonyls, carbamyl, and (C1-C8) alkylsulphonyls; carboxy(C1-C6)alkyls; cyano(C1-C6)alkyls; carbamyl(C1-C6)alkyls; (C1-C6) trifluoroalkyls; tri(C1-C6)alkylsilane-(C1-C6)alkyl radical; a C1-C6 sulphonamidoalkyl radical; a (C1-C6)alkylcarboxy(C1-C6)alkyls; (C1-C6)alkylsulphinyl(C1-C6)alkyls; (C1-C6)alkylsulphonyl(C1-C6)alkyls; (C1-C6)alkylketo(C1-C6)alkyls; Nxe2x80x94(C1-C6)alkylcarbamyl(C1-C6)alkyls; Nxe2x80x94(C1-C6)alkylsulphonamido(C1-C6)alkyls;
x and y are chosen from the integers 0 and 1; with the proviso that:
in the unsaturated cationic groups of formula (II):
when x=0, the linker arm D is attached to the nitrogen atom,
when x=1, the linker arm D is attached to one of the ring members E, G, J and L,
y can take the value 1 only:
1) when the ring members E, G, J and L simultaneously represent a carbon atom and when the radical R9 is borne by the nitrogen atom of the unsaturated ring; or alternatively
2) when at least one of the ring members E, G, J and L represents a nitrogen atom to which the radical R9 is attached;
in the unsaturated cationic groups of formula (III):
when x=0, the linker arm D is attached to the nitrogen atom,
when x=1, the linker arm D is attached to one of the ring members E, G, J, L and M,
y can take the value 1 only when at least one of the ring members E, G, J, L and M is chosen from divalent atoms and when the radical R9 is borne by the nitrogen atom of the unsaturated ring;
in the cationic groups of formula (IV):
when x=0, then the linker arm D is attached to the nitrogen atom bearing the radicals R10 to R12,
when x=1, then two of the radicals R10 to R12 form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring as defined above, and the linker arm D is borne by a carbon atom of the saturated ring;
Xxe2x88x92 is chosen from monovalent and divalent anions; in an embodiment of the invention, Xxe2x88x92 is chosen from halogen atoms such as chlorine, bromine, fluorine, and iodine, a hydroxide, a hydrogenosulphate, and (C1-C6)alkyl sulphates such as, for example, a methyl sulphate or an ethyl sulphate;
it being understood that:
the number of cationic groups Z is at least equal to 1;
when at least one of R4, R5, Rxe2x80x24, Rxe2x80x25, R7, R8, Rxe2x80x27, and Rxe2x80x28 is chosen from Z groups in which the linker arm D is chosen from alkyl chains comprising a ketone function, then the ketone function is not directly attached to the nitrogen atom of the group xe2x80x94NR4R5, xe2x80x94NRxe2x80x24Rxe2x80x25, xe2x80x94NR7R8 or xe2x80x94NRxe2x80x27Rxe2x80x28;
when at least one of R4, R5, Rxe2x80x24, Rxe2x80x25, R7, R8, Rxe2x80x27, and Rxe2x80x28 is the point of a attach of a linker arm B chosen from alkyl chains comprising a ketone function, then the ketone function is not directly attached to the nitrogen atom of the group xe2x80x94NR4R5, xe2x80x94NRxe2x80x24Rxe2x80x25, xe2x80x94NR7R8 or xe2x80x94NRxe2x80x27Rxe2x80x28.
As mentioned above, the colorations which can be obtained with the oxidation dye composition in accordance with the invention can be strong and can produce a wide range of shades and colours. They moreover can have excellent properties of resistance to the action of various external agents (e.g., light, bad weather, washing, permanent-waving, perspiration, friction). These properties can be particularly noteworthy as regards the resistance of the colorations obtained to the action of light, washing, permanent-waving and perspiration.
In formula (I) above, the alkyl and alkoxy radicals can be linear or branched.
Representative rings of the unsaturated groups Z of formula (II) above, include, for example, pyrrole, imidazole, pyrazole, oxazole, thiazole and triazole rings.
Representative rings of the unsaturated groups Z of formula (III) above, include, for example, pyridine, pyrimidine, pyrazine, oxazine and triazine rings.
Compounds of formula (I) above, include, for example:
1,3-bis{3-{3-[(2-aminoanilino)-N-propyl]}-3H-imidazol-1-ium}propane dibromide,
N1,N3-bis[3-N-(2-aminoanilino)propyl]-1,1,3,3-tetramethyldiammonium 1,3-propane dibromide,
1,4-bis{3-{2-[(2-aminoanilino)-N-ethyl]}-3H-imidazol-1-ium}butane dichloride,
1-[2-(2-aminoanilino)ethyl]-3-[-(2-aminoanilino)-propyl]-3H-imidazol-1-ium monochloride, and the acid addition salts thereof.
The compounds of formula (I) in accordance with the invention can be obtained according to methods which are known in the art, for example by reduction of the corresponding cationic nitro compounds (cationic xe2x80x9cdoublexe2x80x9d ortho-nitroanilines).
This reduction step (production of a primary aromatic amine), which may or may not be followed by a salification, is generally, for convenience, the final step of the synthesis.
This reduction can take place earlier in the sequence of reactions leading to the preparation of the compounds of formula (I), however, the primary amine created (for example by an acetylation, benzenesulphonation, etc. step), should be xe2x80x9cprotected,xe2x80x9d for example by known methods, before carrying out the desired substitution(s) or modification(s) (including quaternization) and then the amine function may in the end be xe2x80x9cdeprotectedxe2x80x9d (generally in acidic medium).
When the synthesis is complete, the compounds of formula (I) in accordance with the invention can, if necessary, be recovered by methods which are well known in the state of the art, such as crystallization or distillation.
Another subject of the invention is the use of the compounds of formula (I) and acid addition salts thereof in accordance with the invention as oxidation bases, coupling bases, or even as auto-oxidizing dyes for the oxidation dyeing of keratin fibres, and in of particular human keratin fibres such as the hair.
In an embodiment of the invention, the compounds of formula (I) and acid addition salts thereof are used as couplers for the oxidation dyeing of keratin fibres.
The invention also relates to a composition for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, comprising, in a medium which is suitable for dyeing, at least one ingredient selected from compounds of formula (I) and acid addition salts thereof in accordance with the invention.
In an embodiment of the invention, the at least one ingredient is present in the composition in an amount ranging from 0.0005 to 12% by weight relative to the total weight of the dye composition, particularly the amount ranges from 0.005 to 6% by weight relative to this weight.
According to an embodiment of the invention, the dye composition also includes at least one oxidation base which can be chosen from the oxidation bases conventionally used in oxidation dyeing, including para-phenylenediamines, bis(phenylo)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Representative para-phenylenediamines include, for example, para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-chloroaniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, -(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(xcex2-hydroxyethyl)-para-phenylenediamine, -(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine and N-(xcex2-methoxyethyl)-para-phenylenediamine, and the acid addition salts thereof.
More particularly, the para-phenylenediamines mentioned above can be para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2xcex2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-xcex2-acetylaminoethyloxy-para-phenylenediamine, and the acid addition salts thereof.
Representative bis(phenyl)alkylenediamines include, for example, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-(aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the acid addition salts thereof.
Representative para-aminophenols include, for example, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the acid addition salts thereof.
Representative ortho-aminophenols include, for example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the acid addition salts thereof.
Heterocyclic bases include, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
When they are used, these oxidation bases are present in the dye composition, in one embodiment, in an amount generally ranging from 0.0005 to 12% by weight relative to the total weight of the dye composition, particularly in an amount ranging from 0.005 to 6% by weight relative to this weight.
In addition to the compound(s) of formula (I) and acid addition salts thereof above, the dye composition in accordance with the invention can also include at least one additional coupler which can be chosen from couplers used conventionally in oxidation dyeing, including meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indolene derivatives, pyridine derivatives and pyrazolones, and the acid addition salts thereof.
Specific examples of suitable couplers include 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazol-5-one, and the acid addition salts thereof.
When they are present, these couplers are present in the dye composition, in an embodiment of the invention, in an amount generally ranging from 0.0001 to 10% by weight relative to the total weight of the dye composition, and particularly the amount ranges from 0.005 to 5% by weight relative to this weight.
In general, the addition salts with an acid which can be used in the context of the dye compositions of the invention (compounds of formula (I), additional oxidation bases and couplers) are chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The medium which is suitable for dyeing (or the support) generally is chosen from water and a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in water. Suitable organic solvents include, for example, (C1-C4) lower alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol and phenoxyethanol, similar products and mixtures thereof.
The solvents can be present in an amount generally ranging from 1 to 40% by weight relative to the total weight of the dye composition, particularly in an amount ranging from 5 to 30% by weight.
In an embodiment of the invention, the pH of the dye composition generally ranges from 3 to 12, particularly from 5 to 11. The pH can be adjusted to the desired value using acidifying or basifying agents commonly used to dye keratin fibres.
Suitable acidifying agents include, for example, inorganic and organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.
Suitable basifying agents include, for example, aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (V) below: 
in which W is chosen from propylene residues optionally substituted with a radical chosen from hydroxyl and (C1-C6)alkyls; R14, R15, R16 and R17, which may be identical or different, are chosen from a hydrogen atom, (C1-C8)alkyl radicals and (C1-C6) hydroxyalkyl radicals.
The oxidation dye compositions in accordance with the invention can also include at least one direct dye, in particular to modify the shades or to enrich them with glints.
The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, packaging agents such as, for example, silicones, which may or may not be volatile or modified, film-forming agents, ceramides, preserving agents and opacifiers.
Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the addition(s) envisaged.
The dye composition according to the invention can be in various forms, such as in the form of liquids, creams or gels or in any other form which is suitable for dyeing keratin fibres, and in particular human hair.
The invention also relates to a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, using the dye composition as defined above.
According to this process, at least one dye composition as defined above is applied to the fibres for a period which is sufficient to develop the desired coloration, either in air or using an oxidizing agent. The dye composition can optionally contain oxidation catalysts, in order to accelerate the oxidation process.
According to an embodiment of the process of the invention, the coloration of the fibres can be carried out without addition of an oxidizing agent, merely by contact with atmospheric oxygen, i.e., the air.
According to another embodiment of the process of the invention, at least cone dye composition as defined above is applied to the fibres, the colour being developed at acidic, neutral or alkaline pH using an oxidizing agent which is added to the dye composition just at the time of use, or which is present in an oxidizing composition which is applied simultaneously or sequentially in a separate manner.
According to this embodiment of the dyeing process of the invention, the dye composition described above can be mixed, at the time of use, with an oxidizing composition containing, in a medium which is suitable for dyeing, at least one oxidizing agent present in an amount which is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres and left in place for an amount of time sufficient to develop the desired coloration, after which the fibres are rinsed, washed with shampoo, rinsed again and dried. In an embodiment of the invention, the time period for developing the desired coloration is generally 3 to 50 minutes, and can be 5 to 30 minutes.
The oxidizing agent present in the oxidizing composition and as defined above can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibres, including hydrogen peroxide, urea peroxide, alkali metal bromates and persalts such as perborates and persulphates, and enzymes such as peroxidases and 2-electron oxidoreductases. In an embodiment of the invention, hydrogen peroxide is the oxidizing agent.
In one embodiment of the invention, the pH of the oxidizing composition containing the oxidizing agent as defined above is such that, after mixing with the dye composition, the pH of the resultant composition applied to the keratin fibres generally ranges from 3 to 12, particularly from 5 to 11. The pH is adjusted to the desired value using acidifying or basifying agents commonly used to dye keratin fibres and as defined above.
The oxidizing composition as defined above can also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
The composition which is finally applied to the keratin fibres can be in various forms, such as in the form of liquids, creams, gels or any other form which is suitable for dyeing keratin fibres, and in particular human hair.
Another subject of the invention is a multi-compartment dyeing device or kit or any other multi-compartment packaging system, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition as defined above. These devices can be equipped with a means for delivering the desired mixture onto the hair, such as the devices described in patent FR 2,586,913, the disclosure of which is herein specifically incorporated by reference.